Polyoxyethylene derivatives of sucroglycerides



United States Patent 3,277,080 POLYQXYETHYLENE DERIVATIVES 0F SUCROGLYCERIDES Luciano Nobile, Milan, Italy, assignor to Ledoga, S.p.A., Milan, Italy N0 Drawin Filed .lan. 28, 1964, Ser. No.'"340,807 Claims priority, application Italy, Feb. 8, 1963, 2,716/63, Patent 31,690 7 Claims. (Cl. 260-234) This invention relates to new surfactant agents obtainable from sucroglycerides (that is mixtures of monoand diglycerides with sucrose esters) by means of oxyethylation. More particularly this invention relates to the improved detergent properties shown by said oxyethylenated mixture in comparison with its components which, taken singularly, show lower detergent characteristics.

This is a continuation in part of our copending application Serial Number 192,077 filed on May 3, 1962.

Astonishingly enough the mixture of a pure oxyethylenated sucromonoester and a pure oxyethylenated mono and diglyceride, in determined proportions reach higher detergent values than the single components, thus revealing in the field of the detergents a phenomenon which may be called synergistic such as happens in the pharmacological field.

Sucroglycerides are obtained in known manner (US. Patent No. 2,893,990) by transesterification, in a solvent, of natural triglycerides like lard oil, tallow, coconut, palm oil, palmist oil etc., or synthetic triglycerides, with sucrose in the presence of an alkaline catalyst, such as alkali metal hydroxides and carbonates. During the reaction, one or more acid residues of the glycerides are split and react to fix one or more alcoholic hydroxyls of the sucrose, so that it is esterified. In this way a series of products is obtained having different contents of combined sugar, depending on the quantity of sucrose present in the transesterification. These are called sucroglycerides which are thus composed, in different proportions, of monoesters of sucrose with the different fatty acids contained in the starting glyceride, monoand diglycerides or their mixtures (depending on the quantity of fatty acid residues removed from each mole of the starting glyceride) and variable proportions of unreacted triglyceride. Sucroglycerides are in general water-insoluble products which are, however, easily dispersible; they possess lypophilic properties and consequently, not being particularly good emulsifiers, have comparatively low wetting and detergent properties.

The oxyethylation of synthetic organic products, such as alkylphenols and higher fatty alcohols, or of natural products, such as higher fatty acids and their glycerides, makes it possible to obtain surfactant agents possessing detergent, wetting, foaming and emulsifying properties which vary according to the properties of the starting material and the number of moles of ethylene oxide introduced for each mole of such starting material.

The various oxyethylenated sucroglycerides, if the reaction conditions and the reactants proportions have always been the same, have the same composition whatever was the initial fatty ester used. These reaction conditions consist in a transesterification reaction between a triglyceride and sucrose in a molar ratio varying between l:0.5 and 1:6, using as solvent dimethylformamide Patented Oct. 4, 1966 ice in the presence of an alkaline catalyst which may be sodium or potassium carbonate; the temperatures have to be maintained in a range of to 120 C. for 2-10 hours. The oxyethylenation of the so obtained sucroglycerides is conducted in absence of solvents introducing ethylene oxide in proportions varying from 0.5 to 9 parts per one part in weight of the sucroglyceride. However for obtaining a good detergent the weight ratio between ethylene oxide and the sucroglyceride is 2:1. The temperature which is commonly used for this kind of reaction is comprised between 140 and 160 C. As this would compromise the stability of the sucroglyceride we have found that the temperature must be lowered down about to 130. Thanks to the reproducibility of the composition it has been possible to demonstrate the main property of the oxyethylenated sucroglycerides, that is the synergistic activity shown by the oxyethylenated compounds which, in admixture, show higher detergency values than if taken singularly. This property must he obviously considered in connection with the intrinsic value of the oxyethylenated sucroglycerides which show clearly superior and improved detergent qualities on the normal detergents.

The synergistic activity of the oxyethylenated sucroglycerides has been performed confronting the oxyethylenated tallow sucroglyceride (TOSG) and the oxyethylenated coconut sucroglyceride (COSG) with their single components. Both of the oxyethylenated sucroglycerides have been obtained reacting sucrose and coconut glyceride (respectively tallow glyceride) in a ratio 0.5 :1 and condensing then 1 part in weight of the obtained compound with 2 parts of ethylene oxide.

5 parts in weight of each compound have been admixed with parts in weight of the following builders composition:

Percent Sodium tripolyphosphate 57.50 Sodium metasilicate 8.75 Urea 10.62 Carboxymethyl cellulose 2.50 Sodium sulphate 20.63

Of each composition g. have been dissolved in 1 liter of water (that is a 5% solution of active principle) and the cleaning power of the solution assayed in a Launder- Ometer apparatus against cotton dirtied in a standard way. The washings have been performed at a temperature of 50 C., for a time of 60 minutes. The dirt removed was evaluated with the Lange leucometer. The data are collected in the table 1.

TABLE 1 Detergent: Percent dirt removed COSG 83.5 TOSG 77.5 Sucrose monoester from coconut oil acids oxyethylenated 1:2 72.2 Coconut monoand diglycerides (60:40) oxyethylenated 1:2 61.8 Tallow monoand diglycerides (60:40) oxyethylenated 1:2 47.1

The comparison experiments of the oxyethylenated sucroglycerides with some of the commercial detergents have been conducted performing washing assays both in a laboratory apparatus and in normal washing machines and in measuring the percentage of the dirt removed.

a From these data it appears that the oxyethylenated sucroglycerides possess considerably higher detergent properties than the commercially available detergents.

We shall record here the results obtained using the oxyethylenated tallow sucroglyceride (TOSG), and the oxyethylenated coconut oil sucroglyceride (COSG) (both prepared as previously recorded) admixed with builders in proportions of the %l0%20%, which had the com position recorded in column 2.

The commercially available detergents had the composition:

Bleaching agent.

The detergency assays were performed in a Launder- Ometer at a temperature of 50 C. for 60 minutes. The tissue used was cotton dirtied in a standard way with China ink and olive oil.

The whiteness of the cleaned tissue was evaluated with the Lange leucometer and expressed in percent of removed dirt (average values). The data are collected in the Table 2 in two columns according to the quantity per liter of the detergent.

The data point out that the higher detergency power is possessed by the oxyethylenated sucroglycerides (COSG and TOSG) even when they are contained in the composition in a lower percentage than the active principle of the commercial detergents.

A second series of assays was performed on dirty cotton linen using a 5% TOSG mixture in the builders described in column 2 and compared with a detergent consisting of the same builders and including a 5% of oleocetyl alcohol oxyethylenated 1:25 (OOC). For these practical assays a washing machine Schultess type was used, operating at a temperature of 85 C. Table 3 collects the average data in percent of dirt removed, resulting from Q. a photocolorimetric measurements on blank tissues with standard dirt (TNO Delft test).

TABLE 3 Percent dirt removed with Detergent TOSG. 86 00 00 C 53 It is very interesting to compare the superficial tension values of COSG and TOSG with the ones of nonyl phenol-[-10 moles of ethylene oxide at different concentrations. The data, collected in Table 4 indicate that the oxyethylenated sucroglycerides lower better the superficial tension according to the raising length of the fatty acid'chain. In any case the COSG is a better active surfactant than the well-known oxyethylenated nonyl phenol. The values have been determined by the Lecomte de Nouy method and are expressed in dynes/crn.

TABLE 4 Compounds 0.001 g./l. 0.01 g./l. 0.1 g./1 1 g./l.

Nonyl phenol plus 10 moles of ethyleneoxide. 46. 3 34. 4 35. 4 35. 4 TO S G 47.4 40. E) 39. 5 39. 5 44.6 33. 7 32. 7 32. 8

The biodegradability is a property which is now becoming a fundamental request for a good detergent. The broad use of this class of compounds, the foaming characteristics possessed by a large number of them, their inevitable fate in waste Waters and in consequence, the water pollution of pipes, sewer and rivers, creates important community problems which can be solved only if the detergents do not foam and are easily biodegradable. The oxyethylenated sucroglycerides possess in high degree these properties. The foam is practically unnoticeable at normal temperatures, while assays on their biodegradability show that the bacteria present in the waste water destroy them very rapidly. The biodegradability of oxyethylenated sucroesters has been evaluated by determining the growth of the number of bacteria and the degradation of the detergent. The latter determination was performed following colorimetrically the disappearance of the oxyethylenated residue. It must be however emphasized that TOSG is firstly hydrolysed (in less than one hour) by sewage water and that of all the hydrolysis products (fatty acids, sucrose, glycerol, oxyethylenated sucrose and glycerol), the oxyethylenated residue is the most resistant to degradation. However also this degradation occurs very rapidly, that is in 18 hours as shown in Table 5 where the data comparing degradation of TOSG in Pennassay Difco Broth, Aqua fontis, sewage water show that the sole sewage water has the possibility of destroying completely the detergent. The recorded results are average values of at least 4 assays.

TABLE 5 hours 18 hours 24 hours 48 hours Bacteria, Detergent, Bacteria, Detergent, Bacteria, Detergent, Bacteria, Detergent, per ml. ppm. per ml. p.p.n1. per ml. ppm. per ml. porn.

(1) Pennassay Difco Broth:

(a) With bacteria (control) 4. 240 0 360. 10 0 560. 10 0 (b) With bacteria and detergent 4. 240 44. 5 386. 21. 5 498. 10 0 (0) With bacteria and detergent 4. 240 10. 5 356. 10 4. 5 453. 10 0 (d) With detergent only 0 45. 0 0 44.5 0 45 (e) With detergent only 0 8.0 O 9 0 7 (2) Aqua iontis:

(a) With bacteria (control) 1. 910 0 150.000 0 124. 000 0 (b) With bacteria and detergent 1. 910 45. 5 138. 000 46. 5 123.000 40.5 (c) With bacteria and detergent 1.910 9. 5 148. 000 10. 0 78.000 7. 5 (d) With detergent only 0 45. 0 0 40. 0 0 45. 0 (9) With detergent only 0 8.0 0 8 0 8.0 (3) Sewage water:

(a) 1st assay 550. 000 8. 5 620. 000 0 (b) Znd'assay; 303. 000 9. 0 955. 000 0 Generally, the polyoxyethylenic products have a so Example 6 called cloud point, which is usually lower than 60 C.

When these compounds are used for industrial detergence purposes they have to be admixed with sulfonates which prevent the disappearance of the detergent properties. With the oxyethylenated sucroglycerides which have a cloud point above 90, the presence of another detergent is not necessary, as they may reach the temperature of 90 C.

Example 1 Into a reaction chamber for oxyethylation introduce 100 kg. of tallow sucroglyceride with a content of combined sugar of and 0.800 kg. of sodium hydroxide. Heat at 90 C. and introduce during 4 hours 200 kg. of ethylene oxide.

The temperature must be regulated so as to have at the end of the reaction a maximum temperature of 120 C.

The condensation product is a light brown oily liquid quite and quickly soluble in water, with a cloud point of 93 C. (in solution at 1% concentration in distilled water).

Example 2 Proceed as in Example 1 introducing during 4 hours 300 kg. of ethylene oxide instead of 200. The condensation product is a light brown oily liquid, very soluble in water, with a cloud point of 96 C.

Example 3 Proceed as in Example 1, using coconut oil sucroglyceride with a content of sucrose of Add 0.750 kg. of potassium hydroxide to the 100 kg. of sucroglyceride. Reaction is started at 80 C. and the quantity of ethylene oxide is in the ratio 2:1 in comparison with the starting total weight. The final temperature is 120 C. The total duration of the condensation is 5 hours.

The obtained product (300 kg.) is composed of a pale yellow oily liquid quite soluble in water with a gently foaming solution and with a cloud point at 92 C. (1% solution in distilled water).

Example 4 Proceed as in Example 3, reacting ethylene oxide in a ratio of 3: 1, in weight to the sucroglyceride. The product is a pale yellow oil very soluble in water. Cloud point at 97 C.

Example 5 Into a reaction chamber for oxyethylation introduce 95 kg. of lard sucroglyceride with a content of combined sugar of 25%, 5 kg. of refined tallow and 0.150 kg. of sodium hydroxide. Heat at 90 C. and introduce during 4 hours time 300 kg. of ethyleneoxide.

The temperature must be regulated so as to have at the end of the reaction a maximum temperature of 120 C.

The condensation product is a light brown oily liquid quite and quickly soluble in water, with a cloud point of 100 (in solution at 1% concentration).

Proceed as in Example 5, using coconut oil sucroglyceride with a content of sucrose of 30%. Add 5 kg. of palmist oil and 0.150 kg. of potassium hydroxide to the 95 kg. of sucroglyceride. Reaction is started at C. and the quantity of ethyleneoxide is in the ratio 3:1 in comparison with the starting total weight. The final temperature is 120 C. The total length of the condensation is 5 hours.

The obtained product (400 kg.) is composed of a pale yellow oily liquid quite soluble in water with a greatly foaming solution and with a cloud point at 102 (1% solution in water).

Example 7 Proceed in the same way as in Example 5, provided that the ethyleneoxide introduced is in the ratio of 9:1 on the weight of the mass of lard sucroglyceride and lard. The length of the condensation is 7 hours. The final product obtained is a soft, waxy, ivory-colored mass, quite soluble in water with a cloud point of 110 (1% solution in salt water).

I claim:

1. Condensation products of sucroglycerides with 0.5 to 9 parts by weight of ethylene oxide, said products having surfactant, detergent and emulsifying properties and having a cloud point in aqueous solution from 92 to 97 C.

2. Condensation product of tallow sucroglyceride with 0.5 to 9 parts by weight of ethylene oxide.

3. A condensation product of coconut sucroglyceride with 0.5 to 9 parts by weight of ethylene oxide.

4. Condensation product of 1 part by weight of tallow sucroglyceride, composed of 0.5 part by weight of sucrose to 1 part by weight of tallow glyceride, with 2 parts by weight of ethylene oxide.

5. Condensation product of 1 part by weight of coconut sucroglyceride, composed of 0.5 part by weight of sucrose to 1 part by weight of coconut glyceride, with 2 parts by weight of ethyleneoxide.

6. Condensation products of sucroglycerides with about 3 to 9 parts by weight of ethyleneoxide, prepared in the presence of about 5 parts of triglyceride to parts of the sucr-oglyceride and in the presence of an alkali metal hydroxide, said products having surfactant, detergent, and emulsifying properties, and having a cloud point in 1% aqueous solution of about 100 to 7. A condensation product of lard sucroglyceride with about 3 to 9 parts by weight of ethyleneoxide and about 5 parts of tallow to 95 parts of the lard sucroglyceride, and in the presence of an alkali metal hydroxide.

References Cited by the Examiner UNITED STATES PATENTS 3,018,282 1/1962 Crecelius- 260-234 3,102,114 8/1963 Komori et a1 260-234 LEWIS GOTTS, Primary Examiner. J. R. BROWN, Assistant Examiner. 

1. CONDENSATION PRODUCTS OF SUCROGLYCERIDES WITH 0.5 TO 9 PARTS BY WEIGHT OF ETHYLENE OXIDE, SAID PRODUCTS HAVING SURFACTANT, DETERGENT AND EMULSIFYING PROPERTIES AND HAVING A CLOUD POINT IN AQUEOUS SOLUTION FROM 92 TO 97*C. 